Antimicrobial cleaning composition

ABSTRACT

A novel antibacterial cleaning composition which exhibits exceptional germicidal activity for sustained periods of time is provided. The antibacterial cleaning composition that includes: (a) a quaternary ammonium compound; (b) an anionic polymer having an acid number greater than 10 wherein the anionic polymer is partially or completely neutralized by the quaternary ammonium compound to form a polymer complex and wherein the polymer complex is greater than about 15% by weight of the solids in the composition; (c) a dispersing agent and/or solvent; and (d) water. The composition can be incorporated into the matrix of sponges. Alternatively, the quaternary ammonium compound can be complexed directly to cellulosic sponges that have been functionalized with anionic groups.

FIELD OF THE INVENTION

The present invention relates generally to hard surface cleaners thatare especially effective in household applications and particularly toan antimicrobial cleaning composition that exhibits exceptional andsustained germicidal activity.

BACKGROUND OF THE INVENTION

The use of quaternary ammonium compounds as an antibacterial agent iswell known in the art. See U.S. Pat. Nos. 2,746,928, 3,344,018,3,719,711, and JP 01/46081. For instance, quaternary ammonium compoundshave been incorporated into polymer and liquid compositions to protectthe compositions themselves from microbial attack. See U.S. Pat. Nos.3,471,423, 5,028,619 and 5,399,343. Specifically, U.S. Pat. No.5,399,343 discloses a nail lacquer composition, including a film formingpolymer, in which the improvement comprises the inclusion of a carboxylcellulose neutralized with an antimicrobial quaternary ammoniumcompound. This patent teaches that the polymer/quaternary ammoniumcompound complex be present in an amount no higher than 5% by weight ofthe solids in the composition. Furthermore, quaternary ammoniumcompounds have also been employed as an additive in a variety ofhousehold products including detergents. See U.S. Pat. Nos. 3,093,591,3,560,390, 4,272,395 and 4,576,729. U.S. Pat. No. 4,476,251 disclosesdisposable polyurethane a wiping pad which apparently releasesquaternary ammonium compounds that impart antibacterial activity.

Prior art antimicrobial products tend to exhibit rather weak germicidalactivities. Endeavors to produce products demonstrating sustainedactivities include the use of polymer compositions which formpurportedly abrasion resistant films containing biocides. See, forexample, U.S. Pat. Nos. 3,793,275, 4,883,838, 4,908,381, 5,061,485, and5,108,740. It is believed that these compositions are deficient in atleast two respects. First, while the film may be wear-resistant, itrarely provides the desired antimicrobial activity. Second, the film maybe difficult to remove thereby creating unsightly build-up problems.

SUMMARY OF THE INVENTION

The present invention is based on the discovery of a novel antibacterialcleaning composition which exhibits exceptional germicidal activity forsustained periods of time.

In one aspect, the invention is directed to an antibacterial cleaningcomposition that includes:

(a) a quaternary ammonium compound;

(b) an anionic polymer having an acid number greater than 10 wherein theanionic polymer is partially or completely neutralized by the quaternaryammonium compound to form a polymer complex and wherein the polymercomplex is greater than about 15 % by weight of the solids in thecomposition;

(c) a dispersing agent that is selected from the group consisting of anon-ionic polymer, a surfactant, a water-miscible solvent, and mixturesthereof;

(d) the balance, water.

In another aspect, the invention is directed to a method of impartingantibacterial action on a surface that includes the steps of:

(a) applying the inventive antibacterial cleaning composition onto thesurface; and

(b) allowing water and solvent, if present, to evaporate from thecleaning composition to form a layer of said polymer complex that iscoated on the surface. The polymer complex will provide sustainedgermicidal activity for the surface. However, the polymer complex can bereadily removed if desired by wiping and washing the surface withdetergent to prevent build-up problems. Preferably, the polymer complexcomprises about 0.75% to 20% of the solids in the cleaning composition.

In a further aspect, the invention is directed to a cellulose materialcomprising anionic groups and quaternary ammonium compounds that arecomplexed to said anionic groups.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The invention provides an antibacterial cleaning composition that formsa film on cleaned surfaces to prevent bacterial redeposition orrecontamination. The cleaning composition is particularly suited forhousehold hard surfaces especially in the bathroom and kitchen. However,it is understood that the cleaning composition can be applied on anysurface or article such as fabrics. The aqueous formulation of theantibacterial cleaning composition generally comprises:

(a) a quaternary ammonium compound;

(b) an anionic polymer having an acid number greater than 10 wherein theanionic polymer is partially or completely neutralized by the quaternaryammonium compound to form a polymer complex and wherein the polymercomplex is greater than about 15% by weight of the solids in thecomposition;

(c) a dispersing agent and/or a water-miscible solvent; and

(d) the balance, water.

In a preferred aqueous embodiment, the cleaning composition comprisesapproximately 0.05%-15% of an anionic polymer, 0.025%-8% of a quaternaryammonium compound, and a dispersing agent selected from (i) 0.02%-15% ofa nonionic polymer, (ii) 1%-80% of a water miscible solvent, (iii)0.05%-10% of a surfactant, or mixtures thereof, with the remainder,water. The anionic polymer preferably has an average molecular weight ofabout 2,000 to 1,000,000, and preferably an acid number larger thanabout 10. As used herein the term "acid number" retains its conventionalmeaning and is determined by the number of milligrams of potassiumhydroxide required for the neutralization of the corresponding acids ofthe anionic groups present in one gram of the polymer.

In the cleaning composition, the anionic polymer is partially orcompletely neutralized by the quaternary ammonium compound to form apolymer complex. The cleaning composition is preferably prepared bymixing effective amounts of the anionic polymer and quaternary ammoniumcompound in water with agitation. The dispersing agent and/orwater-miscible solvent is preferably added before the two maincomponents all mixed together. As used herein of the term "dispersingagent" comprises any suitable agent which will cause the polymer complexto be stably distributed substantially homogeneously in the aqueouscomposition. Depending on the particular anionic polymers and quaternaryammonium compounds employed to synthesize the polymer complex, thepresence of cross-linkers, and other variables, the polymer complexcompositions may exist either as an emulsion, suspension, or solution.As used herein, the term "water-miscible solvent" or "solvent" refers tosuitable organic solvents which can solubilize the polymer complex inthe aqueous composition.

In use, the aqueous cleaning composition can be readily applied byconventional dispensing means. Preferably, the composition is sprayed orotherwise applied onto a surface to form an aqueous layer which developsinto a polymer complex layer having sustained antimicrobial activityfollowing evaporation of the water and solvent if present.Alternatively, the cleaning composition can be incorporated into asponge or other suitable reusable article for applying the composition.

For ease of storage and transportation, water and solvent, if present,can be evaporated from the aqueous cleaning composition to form a gel ofthe polymer complex. The aqueous form can be reconstituted from the gelwithout any adverse effect on antibacterial action by dilution withwater. Additional adjuncts in small amounts such as buffers, fragrance,dye and the like can be included to provide desirable attributes of suchadjuncts.

In the specification, effective amounts are generally those amountslisted as the ranges or levels of ingredients in the descriptions whichfollow hereto. Unless otherwise stated, amounts listed in percentage("%'s ") are in weight percent (based on 100% active) of the cleaningcomposition.

1. Anionic polymer

The anionic polymer is derived from monomers having anionic groupsattached thereto. Preferably the polymer has an average molecular weightof about 2,000 to 1,000,000, and preferably from about 5,000 to 150,000,an acid number larger than about 10 and preferably from about 60 to 700.

Preferred anionic polymers are selected from the group consisting of:(1) a homopolymer that is selected from vinyl sulfonate, acrylate,methacrylate, styrene sulfonate, maleate, vinyl sulfate and mixturesthereof; (2) a copolymer that is derived from (i) one or more anionicmonomers that are selected from the group consisting of vinyl sulfonate,acrylate, methacrylate, styrene sulfonate, maleate, vinyl sulfate (ii)one or more nonionic monomers that is selected from vinyl esters, vinylalcohol, vinyl ethers, acrylamide, methacrylamide, alkyl or arylacrylate, alkyl or aryl methacrylate, alkyl or aryl maleate,acrylonitrile, vinyl pyrrolidone, alkenes, such as, for example,styrene, ethylene and propylene, multifunctional acids, polyols,multifunctional amines, multifunctional isocyanates and multifunctionalepoxy compounds; and (3) methylcarboxylate cellulose.

As is apparent, copolymers may comprise nonionic monomers. A preferredcopolymer comprising nonionic and anionic is formed from acrylamide andacrylate monomers. The anionic polymers employed can be in their salt,acid or partially protonated forms.

The solubility of the anionic polymer will depend, in part, on itsaverage molecular weight, acid number, and the solvent employed. Inaddition, the anionic polymer can be crosslinked with commoncrosslinkers such as, for example, carbodiimide, aziridine, polyols,glyoxal, epoxy compounds and transition metal ions, to reduce itssolubility.

Typically, in formulating an aqueous antibacterial cleaning composition,the anionic polymer comprises about 0.05% to 15% and preferably about0.1% to 8% of the composition.

2. Quaternary ammonium compound

Quaternary ammonium compounds are generally considered "broad spectrum"antimicrobial cationic compounds having efficacy against both grampositive (e.g., Staphylococcus sp.) and gram negative (e.g., Escherichiacoli) microorganisms. Thus, the quaternary ammonium compound areincorporated for antibacterial purposes and should be present in amountseffective for such purposes.

The choice of the quaternary ammonium compounds is not critical.Typically they are preferably selected from mono-long-chain,tri-short-chain, tetralkyl ammonium compounds, di-long-chain,di-short-chain tetralkyl ammonium compounds, and mixtures thereof. By"long" chain is meant about C₆₋₃₀ alkyl. By "short" chain is meant C₁₋₅alkyl, preferably C₁₋₃, or benzyl, or C₁₋₃ alkylbenzyl. Preferredmaterials include the BTC series (Stepan Company) such as BTC 2125, andthe Barquat and Bardac series, such as Bardac 2250, from Lonza Chemical.The chains may straight or branched. N-heterocyclic ring compounds arealso considered quaternary ammonia compounds.

Preferred quaternary ammnonium compounds include, for example, C₈₋₂₂dimethyl benzyl ammonium chloride, C₈₋₂₂ dimethyl ethylbenzyl ammoniumchloride, and di C₆₋₂₀ alkyl dimethyl ammonium chloride.

Other appropriate quaternary ammonium compounds includeparadiisobutylphenoxyethoxyethyl dimethyl benzyl ammonium chloride, andother compounds having a protonated N nucleus, such as chlorohexidineand poly(hexamethylene biguanide hydrochloride).

The anionic polymer is completely or partially neutralized by thequaternary ammonium compound to form a polymer complex which retains itsantibacterial activity. Preferably, the polymer complex is greater thanabout 15%, and more preferably ranges from about 40% to about 100% byweight of the solids in the composition. The polymer complex isgenerally prepared by dissolving the anionic polymer in a solventcontaining a dispersing agent, e.g, water and/or alcohol, and adding adesired amount of quaternary ammonium compound to form the polymercomplex. Typically in formulating an aqueous antibacterial cleaningcomposition, the quaternary ammonium compound is about 0.025% to 8% andpreferably about 0.1 % to 5% of the composition. As is apparent, theamount of the quaternary ammonium compound adding will depend, in part,on the acid number of the anionic polymer.

3. Dispersing agent

Liquid formulations of the antibacterial cleaning composition preferablycomprise water and a dispersing agent that is selected from (i) anonionic polymer, or (ii) a surfactant, or mixtures thereof. The amountof dispersing agent employed is not critical but preferably is presentin an effective amount to emulsify or suspend the polymer complex in theliquid formulation.

A. Nonionic polymer

Preferred nonionic polymers include, for example, polyvinyl alcohol,polyvinyl pyrrolidone, polyacrylamide, polyethylene oxide, polypropyleneoxide, polyvinyl acetate, and mixtures thereof. Typically in formulatingan aqueous antibacterial cleaning composition, the nonionic polymer isabout 0.02% to 15% and preferably about 0.5% to 10% of the composition.

B. Surfactant

The surfactant is preferably a nonionic, amphoteric surfactant, ormixtures thereof. Typically in formulating an aqueous antibacterialcleaning composition, the surfactant is about 0.05% to 10% andpreferably about 0.5% to 6% of the composition.

(i) Nonionic surfactants are preferably selected from alkoxylatedalcohols, alkoxylated phenol ethers, and other surfactants oftenreferred to as semi-polar nonionics, such as the trialkyl amine oxides.The alkoxylated phenol ethers include octyl- and nonylphenol ethers,with varying degrees of alkoxylation, such as 1-10 moles of ethyleneoxide per mole of phenol. The alkyl group can vary from C₆₋₁₆, althoughoctyl- and nonyl chain lengths are readily available. Various suitableproducts available from Union Carbide under the trademark Triton, suchas Triton N-57, N-101, N-111, X45, X-100, X-102, from Mazer Chemicalsunder the trademark Macol, from GAF Corporation under the trademarkIgepal, and from Texaco Chemical Company under the trademark Surfonic.The alkoxylated alcohols include ethoxylated, and ethoxylated andpropoxylated C₆₋₁₆ alcohols, with about 2-10 moles of ethylene oxide, or1-10 and 1-10 moles of ethylene and propylene oxide per mole of alcohol,respectively. Exemplary surfactants are available from Shell Chemicalunder the trademark Neodol, and from Huntsman under the trademarkAlfonic. The semi-polar amine oxides are also preferred, although, forthe invention, a mixture of nonionic and amine oxide surfactants canalso be used. The amine oxides, referred to as mono-long chain, di-shortchain, trialkyl amine oxides, have the general configuration: ##STR1##wherein R¹ is C₆₋₂₄ alky, and R² and R³ are both C₁₋₄ alkyl, or C₁₋₄hydroxyalkyl, although R² and R³ do not have to be equal. These amineoxides can also be ethoxylated or propoxylated. The preferred amineoxide is lauryl amine oxide. The commercial sources for such amineoxides are Barlox 10, 12, 14 and 16 from Lonza Chemical Company, Varoxby Witco and Ammonyx by Stepan Co.

Other preferred nonionic surfactants include ethoxylated fatty acidesters which are available under the trademark Ethox from EthoxChemicals, Inc., sorbitan derivatives available under the trademarkTween from ICI Surfactants, and glycerol esters which are availableunder the trademark Polyaldo from Lonza.

A further preferred semi-polar nonionic surfactant isalkylamidoalkylenedialkylamine oxide. Its structure is shown below:##STR2## wherein R¹ is C₅₋₂₀ alkyl, R² and R³ are C₁₋₄ alkyl, ##STR3##or --(CH₂)_(p) --OH, although R² and R³ do not have to be equal or thesame substituent, and n is 1-5, preferably 3, and p is 1-6, preferably2-3. Additionally, the surfactant could be ethoxylated (1-10 moles ofEO/mole) or propoxylated (1-10 moles of PO/mole). This surfactant isavailable from various sources, including from Lonza Chemical Company,as a cocoamidopropyldimethyl amine oxide, sold under the brand nameBarlox C. Additionally semi-polar surfactants include phosphine oxidesand sulfoxides.

(ii) The amphoteric surfactant is typically an alkylbetaine or asulfobetaine. One group of preferred amphoterics arealkylamidoalkyldialkylbetaines. These have the structure: ##STR4##wherein Rhu 1 is C₆₋₂₀ alkyl, R² and R³ are both C₁₋₄ alkyl, although R²and R³ do not have to be equal, and m can be 1-5, preferably 3, and ncan be 1-5, preferably 1. These alkylbetaines can also be ethoxylated orpropoxylated. The preferred alkylbetaine is a cocoamidopropyldimethylbetaine called Lonzaine CO, available from Lonza Chemical Co. Othervendors are Henkel KGaA, which provides Velvetex AB, and Witco ChemicalCo., which offers Rewoteric AMB-15, both of which products arecocobetaines.

4. Water-miscible solvent

Instead of or, in addition to, using the dispersing agent, awater-miscible solvent to solubilize the polymer complex can beemployed. The water-miscible solvent is preferably selected from C₁₋₆alkanol, C₁₋₆ diols, C₃₋₂₄ alkylene glycol ethers, and mixtures thereof.The alkanol can be selected from methanol, ethanol, n-propanol,isopropanol, butanol, pentanol, hexanol, their various positionalisomers, and mixtures of the foregoing. It may also be possible toutilize in addition to, or in place of, said alkanols, the diols such asethylene, propylene and butylene glycols, and mixtures thereof.Preferred solvents that may be used include ethanol, isopropyl alcohol,butanol, amyl alcohol, ethylene glycol ethers, acetone and propyleneglycol ethers.

The alkylene glycol ether solvents can include ethylene glycol monobutylether, ethylene glycol monopropyl ether, propylene glycol n-propylether, propylene glycol monobutyl ether, diethylene glycol n-butylether, dipropylene glycol methyl ether, and mixtures thereof. Preferredglycol ethers are ethylene glycol monobutyl ether, also known asbutoxyethanol, sold as butyl Cellosolve by Union Carbide, and also soldby Dow Chemical Co., 2-(2-butoxyethoxy) ethanol, sold as butyl Carbitol,also by Union Carbide, and propylene glycol n-propyl ether, availablefrom a variety of sources. Another preferred alkylene glycol ether ispropylene glycol, t-butyl ether, which is commercially sold as ArcosolvePTB, by Arco Chemical Co. Typically in formulating an aqueousantibacterial cleaning composition, the water-miscible solvent is about1% to 80% and preferably about 5% to 50% of the composition.

5. Water and Miscellaneous

For liquid formulations, the antibacterial cleaning composition is mostpreferably an aqueous formulation comprising at least about 15%, andmore preferably at least about 40% water.

Furthermore, small amounts of adjuncts can be added for improvingcleaning performance or aesthetic qualities of the cleaner. For example,buffers could be added to maintain a constant pH preferably betweenabout 1.5-14, more preferably between about 8-13. These buffers includeNaOH, KOH, Na₂ CO₃, K₂ CO₃, as alkaline buffers, and phosphoric,hydrochloric, sulfuric acids as acidic buffers, and others. Builders,such as phosphates, silicates, carbonates, sodium chloride, andmagnesium chloride, may be desirable. Further solubilizing materials,such as hydrotropes, e.g., cumene, toluene and xylene sulfonates, mayalso be desirable. Adjuncts for cleaning include additional surfactants,such as those described in Kirk-Othmer, Encyclopedia of ChemicalTechnology, 3rd Ed., Volume 22, pp. 332-432 (Marcel-Dekker, 1983), andMcCutcheon's Soaps and Detergents (N. Amer. 1984), which areincorporated herein by reference. Aesthetic adjuncts include fragrances,such as those available from Givaudan, IFF, Quest, Sozio, Firmenich,Dragoco and others, and dyes and pigments which can be solubilized orsuspended in the formulation, such as diaminoanthraquinones.Water-insoluble solvents may sometimes be desirable as added grease oroily soil cutting agents. These types of solvents include tertiaryalcohols, hydrocarbons (alkanes), pine-oil, d-limonene and otherterpenes and terpene derivatives, and benzyl alcohols. Thickeners, suchas calcium carbonate, sodium bicarbonate, aluminum oxide, and polymers,such as polyacrylate, starch, xanthan gum, alginates, guar gum,cellulose, and the like, may be desired additives. The use of some ofthese thickeners (CaCO₃ or NaHCO₃) is to be distinguished from theirpotential use as builders, generally by particle size or amount used.

The antibacterial cleaning composition may further include an adhesionpromoter such as, for example, a hydroxyl silicone which serves to bindthe polymer complex to a surface.

Incorporation of polymer complex or quaternary ammonium compound intosponge.

The antibacterial cleaning composition can be incorporated into pads orother similar reusable articles having an absorbent and/or adsorbentmatrix. It is advantageous to incorporate the antibacterial composition,since this will prevent or mitigate the microbial contamination of suchmatrix. Preferably, the pads are made from natural and syntheticsponges, e.g., cellular plastic, foam, and rubber sponge. Preferredcommercially available synthetic sponges include polyurethane andcellulose sponges. Cellulose sponges are typically derived fromregenerated cellulose. One method of incorporating the antibacterialcleaning composition is to treat (e.g. soak) the sponge in the liquidformulation and thereafter allow the sponge to dry. The dry polymercomplex residue or layer becomes attached to or associated with thesponge surfaces. Attachment or association occurs through weaknon-chemical bonds.

Alternatively, after soaking the sponge in the liquid formulation,excess formulation can be removed from the sponge and thereafter thesponge can be stored in a moist state for later use without furtherdrying.

Another method of incorporating the polymer complex into a sponge, e.g.,a cellulose sponge is to impregnate a mass of cellulose material withthe anionic polymer. By impregnation is meant that the anionic polymeris thoroughly mixed into the cellulose material. Thereafter, theimpregnated cellulose material is placed into contact with an aqueoussolution containing the quaternary ammonium compound whereby the polymercomplex is formed. Alternatively, the polymer complex can be fabricatedfirst and thereafter it is impregnated into the cellulose mass.

In addition, the sponge, or other absorbent/adsorbent substrate, canhave an abrasive action, either through incorporation within theabsorbent/adsorbent matrix (see Hoover, U.S. Pat. No. 2,958,593), or asan abrasive surface or scrim (see Politzer, U.S. Pat. Nos. 2,804,728,3,080,688, 3,109,703, and 3,142,714; and co-pending application Ser. No.08/532,532, filed Sep. 22, 1995, entitled "Scrubbing Device Comprising aWoven Scrim and Adsorbent Body," of Michael C. Fryan; all of theforegoing are incorporated by reference thereto).

A further method of impregnating the sponge is to expose the sponge toan aqueous mixture containing the anionic polymer for a sufficientamount of time to allow the polymer to become attached to the spongesurface and thereafter adding the quaternary ammonium compound to themixture.

A method of fabricating a sponge with antibacterial properties is tocomplex quaternary ammonium compounds directly onto cellulosic spongesthat have been functionalized with anionic groups. For example, a spongecomprising a negatively-charged cellulosic sponges can be derived by areaction of a chemical agent having a molecular formula of XRY(X=leaving groups such as, for example Cl, Br, OSO₃ ⁻); R=organicmoiety; Y=anionic groups such as COONa) with the sponge cellulose. Anexample of the XRY is ClCH₂ COONa.

Methods for regenerating cellulose to make porous sponges are known inthe art. For example, a viscose cellulose material may be formed bysteeping sheets of cellulose in 181/2% (by weight) sodium hydroxidesolution for a time sufficient to alkalize the cellulose. The resultingalkaline cellulose is mixed with carbon disulfide, for example, and theresulting mixture is agitated until cellulose xanthate is produced. Thisresulting cellulose xanthate is dissolved in a weak sodium hydroxidesolution to produce a viscose cellulose product, typically containingbetween 5% and 7% by weight cellulose, 5% to 6% of alkalinity and about2.3% to 2.6% total sulphur. This unripened material may be mixed withhemp fibers or other suitable reinforcing fibers, typically having anaverage length of about 3/8 to 1/2an inch, (0.95 to 1.27 cm) whilemaintaining the mass at a temperature preferably below about 15° C. forabout 20 minutes. To this mass is added sodium sulfate decahydratecrystals, having an average particle size in accordance with the desiredpore size of the finished sponge. Typically, an average particle size ofthe sodium sulfate decahydrate of about 10 mm will produce a relativelycourse pore device, whereas an average particle size of about 2 mm willproduce a relatively fine pore device,. The mixing is continued forapproximately an additional ten minutes while maintaining a temperatureof 15° C. or less. This mass may then be deposited into molds or formsof any desirable configuration, preferably rectilinear, and coagulated.

The coagulated cellulose sponge may then be washed in hot water toremove the remaining sodium sulfate decahydrate, neutralized in base,such as sodium sulfate decahydrate, neutralized in base, such as sodiumhydroxide solution, and bleached with a water solution containinghypochlorite. The bleached blocks may then be treated in hot oxalic acidand again washed to remove traces of the acids. The blocks or sheets maythen be sprayed with a humectant such as glycerin, PEG, propyleneglycol, urea or mixtures thereof and dried to the desired moisturecontent.

EXPERIMENTAL

In the following experiments, the inventive antimicrobial cleaningcompositions were tested with respect to antimicrobial activity anddelivery efficiency. In Examples 1-2, aqueous formulations comprisingthe components set forth in Table 1 were tested.

                  TABLE 1                                                         ______________________________________                                                      Formulation                                                     Component       1          2       3                                          ______________________________________                                        Copolymer of acrylamide and                                                                   2.4%       --      --                                         sodium acrylate (72:28).sup.1                                                 Polyvinyl       --         --      6.0%                                       pyrolidone                                                                    Sodium polyvinyl                                                                              0.18%      0.18%   --                                         sulfonate.sup.2                                                               Sodium polyacrylate copolymer.sup.3                                                           --         --      0.63%                                      C.sub.14 tetralkyl NCl                                                                        0.5%        0.5%   0.5%                                       ______________________________________                                         .sup.1 Glascol WN15/25 (Allied Colloids)                                      .sup.2 PSVS (Air Products)                                                    .sup.3 Carboset GA 1915 (BF Goodrich)                                    

EXAMPLE 1 Antibacterial Activity

Black colored ceramic tiles each having a surface area of 1 in.² (6.45cm²) were initially sterilized before 0.07 grams of a formulation weresprayed onto the surface of each tile. The tiles were allowed to dry forat least 12 hours before being initially inoculated with 10 μl of a testorganism suspension which provided an initial load of at least 10⁶bacteria on the surface. For the zero hour readings, the bacterialpopulation was measured after 10 minutes of contact time. For lateranalyses, each tile was rinsed and re-inoculated at intervals so thatafter 24, 48, and 72 hours, a tile would have been rinsed andreinoculated 1, 3, and 4 times, respectively. For each rinse, a spraybottle with the nozzle positioned approximately 10 to 12 inches (25.4 to30.5 cm) from the surface of a tile held upright was used. The tile wassprayed with water for about 5 minutes. Following each rinse the tilewas re-inoculated with 10 μl of the test organism suspension. Finally,following the last rinse and re-inoculation, each tile was allowed toincubate for a period up to about 12 hours before being inoculated for afinal time. Thereafter, about 10 minutes later, the bacterial populationwas measured. For example, tiles initially incubated for 72 hoursunderwent 4 rinses and re-inoculations. Following the fourth and finalrinse/re-inoculation cycle, the tile was subject to one finalinoculation as described above before the bacterial population wasmeasured.

The bacterial survival ratio (R) is the ratio of bacterial populationfor the inoculated versus that of an untreated tile. The percentagereduction of bacteria for each sample is set forth in Table 2 is defmedas 1 minus R. As is apparent from the data, the inventive antibacterialcleaning composition provided exceptional long lasting antibacterialactivity as compared to a commercial cleaner.

                  TABLE 2                                                         ______________________________________                                               Reduction of Bacteria (%)                                                     Gram-positive bacteria                                                                      Gram-negative bacteria                                          (S. aureus)   (K. pneumoniae)                                                   0-hr/   24-hrs/ 72 hrs/                                                                             0-hr/ 24-hrs/                                                                             48 hrs/                            Formulation                                                                            no rinse                                                                              1 rinse 4 rinses                                                                            no rinse                                                                            1 rinse                                                                             3 rinses                           ______________________________________                                        1        >99.998 --      >99.995                                                                             >99.998                                                                             --    >99.951                            2        >99.998 99.970  --    >99.999                                                                             99.976                                                                              --                                 3        99.997  99.135  --    >99.999                                                                             99.96 --                                 CAP.sup.1                                                                              99.998  0.0     --    99.41 0.0   --                                 ______________________________________                                         .sup.1 Commercial Antimicrobial Product. (Active ingredients: quaternary      ammonium compound, solvent and water)                                    

EXAMPLE 2 Antibacterial Activity

Formulation 1 from Table 2 was applied onto tiles in the same manner asin Example 1 except that prior to inoculation with K. pneumoniae thetiles were immersed in a bath containing 50 ml of water for 3 minutes.Thereafter, the bacterial population of the tiles (without anyincubation) were measured. The percentage of reduction for bacterial wasabout 99.49%. In contrast, similarly tested tiles sprayed with theCommercial Antimicrobial Product exhibited essentially 0% reduction.

EXAMPLE 3 Antibacterial Activity of Sponge Delivery System

Various aqueous formulations of the inventive cleaning compositionhaving the components set forth in Table 3 were incorporated intocellulose sponges. The sponges employed were each about 5 x 7 x 1 (in.)(12.7 x 17.78 x 2.54 (cm)) in dimension. For formulations 1-4, 100 gramsof the formulation were soaked into sponges which were then air dried.For formulation 5, the sponge was soaked into 100 grams of a solutioncontaining the anionic polymer. The sponge was then air dried. Next, thesponge was soaked into 100 grams of an aqueous solution containing thequaternary ammonium component and crosslinking agent (glyoxal).Thereafter, the sponge was air dried. For formula 6, the sponge wassoaked into 100 grams of a solution containing the antibacterialcleaning formulation. Thereafter, enough solution was removed so thatthe sponge contained approximately 20 grams of the aqueous antibacterialcleaning formulation remaining therein. The moist sponge was stored in aplastic bag.

                  TABLE 3                                                         ______________________________________                                               Formulation                                                            Component                                                                              1       2       3     4     5     6                                  ______________________________________                                        C.sub.12-16 benzyl                                                                      1.3%   --       1.3% --     1.3% --                                 dimethyl NCl.sup.1                                                            DiC.sub.10                                                                             --       1.3%   --     1.3% --      2%                               dimethylNCl.sup.2                                                             Sodium poly-                                                                           0.47%   0.47%   --    --    --    0.42%                              vinyl sulfonate                                                               Sodium   --      --      0.37% --    --    --                                 polyacrylate.sup.3                                                            Polyacrylic                                                                            --      --      --    0.37% --    --                                 acid.sup.4                                                                    Copolymer of                                                                           --      --      --    --    0.61% --                                 acrylic acid and                                                              acrylamide.sup.5                                                              Copolymer of                                                                           --      --      --    --    --     2.6%                              acrylamide and                                                                sodium                                                                        acrylate.sup.6                                                                Glyoxal.sup.7                                                                          --      --      --    --    0.07% --                                 NaCO.sub.3                                                                             --      --      --    --     0.3% --                                 Isopropyl                                                                                40%     40%     40%   40% --    --                                 alcohol                                                                       ______________________________________                                         .sup.1 Barquat MB50 (Lonza)                                                   .sup.2 Bardac 2280 (Lonza)                                                    .sup.3 Acusol 504N (Rhom & Haas)                                              .sup.4 Glascol E11 (Allied Colloids)                                          .sup.5 Glascol WN33 (Allied Colloids)                                         .sup.6 Glascol WN 15/25 (Allied Colloids)                                     .sup.7 (Aldrich Chemical)                                                

Sponges designated 1-5 which correspond to the particular antibacterialformulation which is incorporated therein were tested for their abilityto deliver antibacterial activity. The sponges were subject to one ofthree water pretreatment regiments: (1) a pre-rinse, (2) squanching, or(3) machine wash. In the pre-rinse, a sponge was placed intoapproximately 300 ml of water and allowed to soaked with water. Excesswater was then manually squeezed from the sponge. This was repeated 5times with fresh water. In squanching, a proprietary and automateddevice which included a chamber and rotable arm that included a presserthat held the sponge was employed. Water continuously flowed through thesponge during the squanching procedure. The cyclic movement of the armpressed the sponge against a surface of the container. Ivory dishdetergent (Procter & Gamble) was applied to the sponge at the beginningof the procedure and after the first 500 cycles. Squanching lasted forabout 20 minutes after about 2000 cycles of the arm. Finally, a regularwashing machine was used in the last pretreatment. Each sponge wassubject to 2 full wash cycles. The first was with detergent and thesecond without.

Sponges were inoculated with bacteria that comprise a composite of S.aureus, P. aruginosa, E. coli, and S. choleraesuis. After inoculationthe sponges were placed in plastic bags at 30° C. for 24 hours. Thebacteria population for the sponges were measured before (I_(o)) andafter (I_(f)) incubation. As is apparent from the data in table 4, thesponges maintain antibacterial activity even after being subjected tothe pre-rinsing, squanching, and machine washing.

                  TABLE 4                                                         ______________________________________                                        Test         Pre-           Machine                                           No.  Sponge  rinsed  Squanched                                                                            washed I.sub.o                                                                              I.sub.f                             ______________________________________                                        1    1       yes     --     --     1.7 × 10.sup.6                                                                 <10                                 2    1       --      yes    --     1.1 × 10.sup.6                                                                 <10                                 3    1       --      --     yes    1.8 × 10.sup.6                                                                 3.0 × 10.sup.5                4    2       yes     --     --     1.6 × 10.sup.6                                                                 <10                                 5    2       --      yes    --     1.2 × 10.sup.6                                                                 <10                                 6    3       yes     --     --     1.1 × 10.sup.6                                                                 <10                                 7    3       --      yes    --     1.7 × 10.sup.6                                                                 2.0 × 10.sup.4                8    4       yes     --     --     1.6 × 10.sup.6                                                                 100                                 9    4       --      yes    --     1.6 × 10.sup.6                                                                 4.0 × 10.sup.3                10   5       yes     --     --     1.5 × 10.sup.6                                                                 <10                                 11   5       --      yes    --     1.0 × 10.sup.6                                                                 6.0 × 10.sup.3                12   6       --      yes    --     1.1 × 10.sup.6                                                                 6.8 × 10.sup.3                13   un-     --      --     --     1.6 × 10.sup.6                                                                 6.0 × 10.sup.8                     treated                                                                       sponge                                                                   ______________________________________                                    

EXAMPLE 4 Odor Control of Sponge Delivery System

Aqueous formulations 1-5 of the antibacterial cleaning composition setforth in Table 5 were incorporated into cellulose sponges by the singlesoaking step as described in Example 3. For aqueous formula 6, theantibacterial cleaning composition was incorporated by soaking thesponge in 100 grams of the composition and thereafter squeezing excesscomposition from the sponge. The moist sponge was stored in a plasticbag before being used.

                  TABLE 5                                                         ______________________________________                                               Formulation                                                            Component                                                                              1       2       3     4     5     6                                  ______________________________________                                        C12-16 benzyl                                                                           1.3%   --      1.0%   1.3%  1.3% --                                 dimethyl NCl.sup.1                                                            DiC.sub.10                                                                             --      1.0%    --    --    --      2%                               dimethylNCl.sup.2                                                             Sodium   0.47%   0.36%   0.36% --    --    --                                 polyvinyl                                                                     sulfonate                                                                     Sodium   --      --      --     0.48%                                                                               0.48%                                                                              0.42%                              polyacrylic                                                                   acid.sup.3                                                                    Copolymer                                                                              --      1.3%    2.6%  --    --    --                                 of acrylic                                                                    acid and                                                                      acrylamide.sup.4                                                              Copolymer of                                                                           --      --      --    --    --     2.6%                              acrylamide and                                                                sodium acrylate                                                               Isopropyl                                                                                40%   --      --    --    --    --                                 alcohol                                                                       Multifunctional                                                                        --      --      --     0.39%                                                                               0.1% --                                 carbodimide.sup.6                                                             HCl      --      --      --    0.033%                                                                              0.033%                                                                              --                                 ______________________________________                                         .sup.1 Barquat MB50 (Lonza)                                                   .sup.2 Bardac 2280 (Lonza)                                                    .sup.3 Glascol F11 (Allied Colloids)                                          .sup.4 Glascol WN15/25 (Allied Colloids)                                      .sup.5 Glascol WN 15/25 (Allied Chemicals)                                    .sup.6 Ucarlink (Union Carbide)                                          

The sponges were subject to squanching as described in Example 3. Eachsponge was then inoculated with a bacterial composite comprising E.aerogenes, P. aruginosa, P. mirabilis, S. aureus and 1% nutrient.Thereafter the sponge was incubated in a plastic bag at 30° C. for 24hours.

The sponges were graded by a panel of expert graders to determinedwhether the sponges significantly reduced odor as compared tobiocideless sponges. All sponges treated with the antibacterial cleaningcomposition demonstrated odor reduction as compared to untreated spongeswhich did not.

The foregoing has described the principles, preferred embodiments andmodes of operation of the present invention. However, the inventionshould not be construed as being limited to the particular embodimentsdiscussed. Thus, the above-described embodiments should be regarded asillustrative rather than restrictive, and it should be appreciated thatvariations may be made in those embodiments by workers skilled in theart without departing from the scope of the present invention as definedby the following claims.

What is claimed is:
 1. An antibacterial cleaning compositioncomprising:a) a quaternary ammonium compound; b) an anionic polymerhaving an acid number greater than 10 wherein the anionic polymer ispartially or completely neutralized by quaternary ammonium compound toform a polymer complex and wherein the polymer complex and wherein thepolymer complex is greater than about 15% by weight of the solids in thecomposition; c) a dispersing agent, which comprises a surfactant that isselected from the group consisting of nonionic surfactant, amphotericsurfactant, and mixtures thereof and; d) optionally, a solvent.
 2. Thecleaning composition of claim 1 wherein the cleaning composition is anaqueous composition which comprises a dispersing agent that comprises anonionic polymer that is selected from the group consisting of polyvinylalcohol, polyvinyl pyrrolidone, polyacrylamide, polyethylene oxide,polypropylene oxide, polyvinyl acetate, and mixtures thereof.
 3. Thecleaning composition of claim 1 further comprises an adhesion promoter.4. A sponge device having antibacterial activity that comprises:(a) asponge; and (b) a polymer complex comprising a quaternary ammoniumcompound and an anionic polymer having an acid number of greater than 10wherein the anionic polymer is partially or completely neutralized bythe quaternary ammonium compound to form the polymer complex which isattached to a surface of the sponge.
 5. A cellulose sponge materialcomprising anionic groups on a surface of the sponge and quaternaryammonium compounds that are complexed to said anionic groups.
 6. Anabsorbent or adsorbent matrix having antibacterial activity, said matrixcomprising;(a) the absorbent or adsorbent matrix, and; (b) a polymercomplex comprising a quaternary ammonium compound and an anionic polymerhaving an acid number of greater than 10 wherein the anionic polymer ispartially or completely neutralized by the quaternary ammonium compoundto form the polymer complex which associates with said matrix.
 7. Thematrix of claim 6 wherein said matrix comprises a sponge.
 8. The matrixof claim 7 wherein said polymer complex is impregnated within saidsponge.
 9. The matrix of claim 7 wherein said polymer complex isprovided in a layer adhered to said sponge.
 10. The matrix of claim 7wherein said polymer complex comprises a component of said sponge.
 11. Amethod of fabricating an absorbent or adsorbent matrix havingantimicrobial activity which comprises the steps of:(a) providing anabsorbent or adsorbent matrix; (b) contacting said matrix with anaqueous mixture comprising an antibacterial cleaning compositioncomprising:(i) a quaternary ammonium compound; (ii) an anionic polymerhaving an acid number greater than 10 wherein the anionic polymer ispartially or completely neutralized by the quaternary ammonium compoundto form a polymer complex and wherein the polymer complex is greaterthan about 15% by weight of the solids in the composition; (iii)optionally a dispensing agent; and (iv) optionally, a solvent;whereinthe polymer complex is associated with a surface of the matrix.
 12. Themethod of claim 11 wherein the matrix comprises cellulose.
 13. Themethod of claim 12 wherein said polymer complex is prefabricated andthereafter incorporated into said matrix.
 14. A method of fabricating anabsorbent or adsorbent matrix having antimicrobial activity whichcomprises the steps of:(a) providing an absorbent or adsorbent matrix;(b) impregnating an anionic polymer into the matrix to form animpregnated matrix; and (c) contacting the impregnated matrix with anaqueous solution of quaternary ammonium compound whereby the anionicpolymer is partially or completely neutralized by the quaternaryammonium compound to form a polymer complex which associates with saidmatrix.
 15. The method of claim 14 wherein the matrix is regeneratedcellulose.